JP2017106022A - Silane terminated polymer for coating, adhesive, sealant and elastomer applications - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copolymer-filled crosslinkable silane-terminated polymer having at least one crosslinkable silyl group in each molecule.SOLUTION: The copolymer-filled crosslinkable silane-terminated polymer is the reaction product of a copolymer-filled polyol and an isocyanate capped hydrosilylated polymer. The isocyanate capped hydrosilylated polymer is the reaction product of at least one isocyanate and a hydrosilylated polymer. The hydrosilylated polymer is the reaction product of a polymer having at least one unsaturated group and at least one alcoholic group in each molecule and a compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule. The copolymer-filled crosslinkable silane-terminated polymers exhibit improved modulus and tensile strength properties while maintaining elongation properties.SELECTED DRAWING: None

Description

  Embodiments of the present invention relate to silane-terminated polymers and methods for making the same.

Crosslinkable silane-terminated polymers (STP) are widely used as raw polymers in coating materials, adhesives, sealing materials, elastomers, etc. (CASE applications) for architectural or industrial applications. STP typically contains polyether polyols and vulcanizable alkoxysilane end groups. The mechanical property requirements of the cured STP vary considerably depending on the end use. One conventional method of producing STP with improved mechanical properties, such as higher modulus and tensile strength, increases the functionality of the polyether polyol.
And / or reducing the equivalent of polyol. However, the improvements in modulus and tensile strength achieved using conventional methods have been obtained at the expense of elongation loss. Therefore, there is a limit to the improvement in modulus that can be achieved using conventional methods.

Accordingly, there is a need for crosslinkable silane-terminated polymers that have improved modulus and tensile strength properties while maintaining elongation properties, and methods for making such silane-terminated polymers.

Embodiments of the present invention provide crosslinkable silyl group-containing polymers that can be made using copolymer-filled polyols. In one embodiment, a copolymerized crosslinkable silane-terminated polymer having at least one crosslinkable silyl group in each molecule is provided. A copolymerized crosslinkable silane-terminated polymer is a reaction product of a copolymerized polyol and an isocyanate-capped hydrosilylated polymer. The isocyanate-capped hydrosilylated polymer is a reaction product of at least one isocyanate and a hydrosilylated polymer. The hydrosilylated polymer is
A reaction product of a polymer having at least one unsaturated group and at least one alcohol group in each molecule, and a compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule.

In yet another embodiment, a method of making a composition comprising a copolymerized crosslinkable silane-terminated polymer having at least one crosslinkable silyl group in each molecule is provided. This method
Providing a polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule and having a number average molecular weight between about 100 and about 5,000, hydrogen in each molecule Adding a compound having a silicon bond and a crosslinkable silyl group and a hydrosilylation catalyst to the polymer, thereby carrying out a hydrosilylation reaction to form a composition comprising the hydrosilylated polymer; Capping the hydrosilylated polymer to form a composition comprising the isocyanate-capped hydrosilylated polymer by exposure to at least one isocyanate having an index between about 100 and about 250, and the isocyanate-capped hydrosilylated polymer By reacting a copolymer containing polyol comprises forming a composition comprising a crosslinkable silane-terminated polymer.

In order that the above-described features of the present invention may be understood in detail, a more specific description of the invention, briefly summarized above, may be had by reference to the embodiments, with some of the embodiments being described. This is illustrated by the attached drawings. However, since the present invention may accept other equally effective embodiments, the accompanying drawings merely illustrate exemplary embodiments of the invention and, therefore, limit the scope of the invention. Note that it should not be considered to do.

Moisture uptake after water aging test of several silane-terminated polymers based on copolymerized polyols (CPP), formed according to embodiments described herein, to silane-terminated polyethers It is the figure which compares quantity. Comparison of water uptake after water aging testing of several silane-terminated polymers based on copolymerized polyols (CPP) cured with various catalysts according to embodiments described herein. It is a figure.

To facilitate understanding, the same reference numerals will be used where possible to designate identical elements that are common to the figures. Elements disclosed in one embodiment are not specifically listed,
It is contemplated that it can be beneficially utilized in other embodiments.

Embodiments of the present invention provide silane-terminated polymers (STP) made using copolymerized polyols and methods for making the same.

Copolymer polyol (CPP) is a filled polyol that usually includes a polyether polyol matrix and a solid phase copolymer. The solid phase copolymer consists of finely dispersed particles,
For example, it typically contains styrene-acrylonitrile, acrylonitrile, polyurea (PHD) solid polymer, and polyurethane-urea particles (PIPA). The solid phase copolymer may be chemically grafted to the polyether backbone. Copolymer polyols are typically produced by polymerizing one or more ethylenically unsaturated monomers dissolved or dispersed in a polyol (feedstock polyol) in the presence of a free radical catalyst, and are stable polymers in the polyol. A dispersion of particles is formed. Other possible components of the CPP include initiators, chain transfer agents, and stabilizers.

In the embodiments described herein, STP derived from CPP and methods of forming STP are provided. By using a copolymerized polyol, an STP with improved modulus and tensile strength is realized without substantial loss of elongation. Compared to conventional methods of improving modulus and tensile strength, the embodiments described herein are
To increase the mechanical performance of what is currently achievable. Furthermore, the use of a copolymerized polyol results in a final product that retains performance over time, as opposed to the loss of properties over time when using conventional fillers.

Embodiments described herein can be employed in any method of manufacturing STP,
The novel composition of the silane end-capped polymer containing the copolymer polyol is described in detail. One exemplary method includes (1) hydrosilylation of allyl monool, (2) end-capping of the hydrosilylation intermediate with diisocyanate, and (3) cupping of the isocyanate intermediate with copolymerized polyol (cPP). A three-stage method involving rings. Compositions useful for making copolymerized STP, i.e. cPP-STP, are cPP polyols, isocyanates, silanes, and allyl polymers.

As used herein, the term “hydrosilylation efficiency” = [100 × ((number of hydrosilylated unsaturated groups on the polyol) / (unsaturation on polyol initially available for hydrosilylation) The total number of groups))] can be determined using ¹ H-NMR or IR spectroscopy.

Hydrosilylation:
In certain embodiments described herein, copolymerized STP can be obtained by hydrosilylation of a polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule. The hydrosilylated polymer can then be capped by exposing it to at least one isocyanate to form a composition comprising the isocyanate capped hydrosilylated polymer. The isocyanate-capped hydrosilylated polymer can then react with a copolymerized polyol to form a copolymerized STP.

The polymer having at least one unsaturated group and at least one alcoholic hydroxyl group is not particularly limited, and includes at least one unsaturated group (such as a carbon-carbon double bond or carbon-carbon triple bond) and at least one alcoholic group. Any polymer can be included as long as it contains hydroxyl groups.

The polymer having at least one unsaturated group and at least one alcoholic hydroxyl group is 40 to 20,000 g / mol, more preferably 200 to 10,000 g.
/ Mol, most preferably having a molecular weight of 800 to 2,000 g / mol.

The polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule can have a number average molecular weight between about 100 and about 5000. All individual values and subranges from 100 to 5000 are included herein and disclosed herein. For example, the number average molecular weight is 100, 200, 300, 4
From the lower limit of 00, 500, 600, 700, 800, 900, 1000, 1250, 1500 or 1750, independently 1000, 1250, 1500, 1750, 2000, 2
Up to an upper limit of 500, 3000, 3500, 4000, 4500, or 5000.

In one embodiment, a polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule is filed on May 27, 2010, which is incorporated herein by reference in its entirety. , "Methods for Producing
Crosslinkable Silyl Group-Containing Pol
Polyoxyalkylene polymers described in co-pending PCT patent application No. PCT / US11 / 038065 entitled “oxyalkylene Polymers”.

In one embodiment, the polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule is combined with an epoxy compound, an unsaturated group-containing and active hydrogen-containing compound as a polymerization initiator in the presence of a catalyst. It can be prepared by performing ring-opening polymerization using This polymerization catalysis may be anionic or cationic, and may be a catalyst such as KOH, CsOH, boron trifluoride, or a complex cyano complex such as zinc hexacyanocobaltate or a quaternary phosphazenium compound ( DMC) catalyst is used.
Active hydrogen-containing compounds that can be used as a polymerization initiator are not limited to the following,
It can be any compound applicable together with a double metal cyano complex, for example a compound containing an alcoholic hydroxyl group, a phenolic hydroxyl group or a carboxyl group.

Polymers having at least one unsaturated group and at least one alcoholic hydroxyl group are allyl alcohol, methallyl alcohol, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, glycerol monoallyl ether, glycerol diallyl ether, Ethylene oxide adducts or propylene oxide adducts and similar compounds containing at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule, hydroxyl-terminated hydrocarbon compounds such as hydroxyl-terminated polybutadiene, and the like can be included. Such active hydrogen-containing compounds that act as polymerization initiators may be used alone or in combination of two or more thereof.

Monoepoxides that can be used for ring-opening polymerization include monoepoxides having no unsaturated groups such as ethylene oxide, propylene oxide, butene oxide, isobutene oxide, epichlorohydrin and styrene oxide, and allyl glycidyl ether , Methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monooxide and cyclopentadiene monoxide containing monoepoxides. These may be used alone or in combination of two or more thereof.

In one embodiment, the polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule has a number average molecular weight between about 600 and about 100 and an OH number between about 50 and about 90. Propylene glycol monoallyl ether having

A polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule is reacted with a compound having a hydrogen-silicon bond and a crosslinkable silyl group in the presence of a hydrosilylation catalyst. May be hydrosilylated by

A compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule can be represented by the following general formula (I).
^{_{H- (Si (R 1 2-}} b) (X b) O) m Si (R 2 3-a) X a (I)
Wherein R ¹ and R ² are the same or different, each from an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms, or 7 Represents an aralkyl group containing 20 carbon atoms, or a triorganosiloxy group represented by R ³ ₃ SiO—, and when there are a plurality of R ¹ groups or R ² groups, they may be the same or different; ³ is a monovalent hydrocarbon group containing 1 to 20 carbon atoms, the three R ³ groups may be the same or different from each other, and X is a hydroxyl group or hydrolyzable group When two or more X groups are present, they are the same or each other (each
other) or may be different from each other, a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and the —SiR ¹ _2-b ) (X _b ) O— group in m b may be the same or different from each other or different from each other, and m represents an integer of 0 to 19, provided that a + Σb ≧ 1 is satisfied. )

The hydrolyzable group represented by X can be any hydrolyzable group known in the art (eg, halogen atoms as well as alkoxy groups, acyloxy groups, ketoximato groups, amino groups, amide groups, acid amide groups, aminoxy groups). Group, mercapto group and alkenyloxy group). Of these, alkoxy groups such as methoxy, ethoxy, propoxy and isopropoxy are preferred from the viewpoint of mild hydrolyzability and ease of handling. One to three such hydrolyzable groups can be bonded to one silicon atom, and the total (a + Σb) is preferably 1 to 5. When two or more hydrolyzable groups are present, they may be the same or different from each other or from each other. The number of silicon atoms in the crosslinkable silyl group can be about 1 to 30.

In some embodiments, the compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule represented by the general formula (I) may include a compound represented by the general formula (II). .
H-Si (R ⁴ _3-c ) (X _c ) (II)
Wherein R ⁴ is an alkyl containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms, or an aralkyl group containing 7 to 20 carbon atoms,
Or represents a triorganosiloxy group represented by R ³ ₃ SiO—, and when there are a plurality of R ⁴ groups, they may be the same or different and R ³ is a monovalent containing 1 to 20 carbon atoms The three R ³ groups may be the same or different from each other, X represents a hydroxyl group or a hydrolyzable group, and when two or more X groups are present, they are the same, They may be different from each other, and c represents 1, 2 or 3. )

Specific examples of the compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule include trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane, trimethylsiloxymethylchlorosilane, and 1,1,3,3-tetramethyl. -1-
Halosilanes such as bromodisiloxane, trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethylsiloxymethylmethoxysilane and alkoxysilanes such as trimethylsiloxydiethoxysilane, methyldiacetoxysilane, phenyl Acyloxysilanes such as diacetoxysilane, triacetoxysilane, trimethylsiloxymethylacetoxysilane and trimethylsiloxydiacetoxysilane, bis (dimethylketoxymato) methylsilane, bis (cyclohexylketoximato) methylsilane, bis (diethylketoxymato) trimethylsiloxysilane, Such as bis (methylethylketoxymato) methylsilane and tris (acetoxymato) silane Tokishimatoshiran, alkenyloxy silane such as methyl isopropenyl silane, such as functional silanes and isocyanate silanes and the like. Among these, alkoxy silanes such as methyldimethoxysilane, trimethoxysilane, methyldiethoxysilane, and triethoxysilane, and halosilanes such as trichlorosilane and methyldichlorosilane are preferable in terms of mild reactivity and ease of handling. preferable.

After reacting with an unsaturated group in a hydrosilylation manner, the halogen atom (s) in the halosilane is converted to an active hydrogen-containing compound such as a carboxylic acid, oxime, amide or hydroxylamine by any suitable method known in the art. Or can be converted to some other hydrolyzable group (s) by reaction with a ketone-derived alkali metal enolate.

The hydrosilylation catalyst can be any metal complex of a metal selected from among Group VIII transition metals such as platinum, rhodium, cobalt, palladium and nickel.
From the viewpoint of hydrosilylation reactivity, H ₂ PtCl ₆ . 6H ₂ O, platinum-divinylsiloxane complex, platinum-olefin complex, Pt metal, RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh /
Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ . 2H ₂ O
, NiCl ₂ , TiCl _{4 and the} like are preferable, and H ₂ PtCl ₆ . 6H ₂ O, platinum-vinylsiloxane complex and platinum-olefin complex are more preferable, and platinum-vinylsiloxane complex and platinum-olefin complex are particularly preferable. The platinum-vinylsiloxane complex collectively refers to a compound formed by coordination of an intramolecular vinyl-containing siloxane, polysiloxane or cyclic siloxane as a ligand with a platinum atom. As typical examples of the ligand, 1,1,3,
Examples thereof include 3-tetramethyl-1,3-divinylsiloxane. Specific examples of the olefin ligand in the platinum-olefin complex include 1,5-hexadiene, 1,7-
Mention may be made of octadiene, 1,9-decadiene, 1,11-dodecadiene and 1,5-cyclooctadiene. Among the ligands specifically mentioned above, 1,1,3,3-tetramethyl-1,3-divinylsiloxane and 1,9-decadiene are preferred from the viewpoint of hydrosilylation reactivity. The hydrosilylation catalyst used in the practice of the present invention may be used alone or in combination of a plurality of chemical species.

The amount of hydrosilylation catalyst used is not particularly limited, but generally the metal in the catalyst per 100 parts by weight of polyoxyalkylene polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule. 0.0000 based on weight
1-1 part by weight, preferably 0.00005-0.05 part by weight, more preferably 0.000
1 to 0.01 parts by weight. If the amount is less than 0.00001 parts by weight, in some cases, no sufficient reaction activity may be obtained, and more than 1 part by weight may be economically disadvantageous, or certain types of In some cases, this may cause discoloration of the polymer.

In the above reaction, the use of a solvent is essentially unnecessary. However, a solvent can be used to uniformly dissolve the catalyst and / or substrate, to control the temperature of the reaction system, and / or to facilitate the addition of the substrate and / or catalyst components. Suitable solvents for such purposes include, but are not limited to, hydrocarbon compounds such as hexane, cyclohexane, ethylcyclohexane, heptane, octane, dodecane, benzene, toluene, xylene and dodecylbenzene, chloroform, methylene chloride, chlorobenzene and o. -Halogenated hydrocarbon compounds such as dichlorobenzene, especially ethyl ether,
Ethers such as tetrahydrofuran and ethylene glycol dimethyl ether are included. Plasticizers that can be used as plasticizers for polyoxyalkylene polymers such as phthalates and polyethers can also be used as reaction solvents. These may be used alone or in combination of two or more thereof.

Although the temperature of hydrosilylation reaction is not specifically limited, For example, it can be in the range of 0 to 150 degreeC, or between the range of 20 to 100 degreeC. Below 0 ° C., the reaction rate may be slow in some cases, and above 150 ° C., in some cases, side reactions involving hydroxyl groups, hydrogen-silicon bonds and / or crosslinkable silyl groups. May progress. In one embodiment, the temperature of the hydrosilylation reaction is about 60 ° C.

In an embodiment of the invention, the polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule has a hydrosilylation rate of at least about 70%, such as between about 70% to about 100%. Hydrosilylated. All individual values and subranges from about 70 to about 100 are included herein and disclosed herein. For example, the hydrosilylation rate is independently about 80%, 85%, 90%, 92%, 94%, 95%, 96% from a lower limit of about 70%, 75%, 80%, 90% or 92%. 98%
Up to an upper limit of 99% or 100%. This includes polymers hydrosilylated at a hydrosilylation rate of 80% to 95% and further include hydrosilylated polymers capped at a hydrosilylation rate of 85% to 95%. As used herein, “hydrosilylation rate” = [100 × ((number of hydrosilylated unsaturated groups on the polyol) / (total number of unsaturated groups on the polyol initially available for hydrosilylation) ))] Can be measured using ¹ H-NMR.

The hydrosilylated polymer produced by the above method and having at least one crosslinkable silyl group and at least one hydroxyl group in each molecule (hereinafter referred to as “hydrosilylated polymer”) reacts with water or atmospheric moisture. Can provide a cross-linked cured product and is therefore useful as a raw material or raw material intermediate for materials such as seals, adhesives, coatings, etc. or compositions for architectural or industrial applications. However, a high percentage (%) of residual hydroxyl groups of this polymer having at least one crosslinkable silyl group and at least one hydroxyl may be capped with a polyisocyanate compound.

Capping:
Among the capping agents that can be used in the embodiment of the present invention, polyisocyanate compounds, that is, compounds having two or more isocyanato groups in each molecule are not limited to the following, but are aliphatic isocyanates and alicyclics. Includes isocyanates, aryl aliphatic isocyanates and aromatic isocyanates.

Examples of suitable aromatic isocyanates include diphenylmethane diisocyanate (MDI)
4,4'-, 2,4 'and 2,2'-isomers, blends thereof and polymeric and monomeric MDI blends, toluene-2,4- and 2,6-diisocyanate (TDI), m- And p-phenylene diisocyanate, chlorophenylene-2,4-
Diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanate-3,3′-dimethyldiphenyl, 3-methyldiphenyl-methane-4,4′-diisocyanate and diphenyl ether diisocyanate, and 2,4,6- Triisocyanatotoluene and 2,4,4'-triisocyanatodiphenyl ether are included.

Isocyanate mixtures such as the commercially available 2,4- and 2,6-isomer mixtures of toluene diisocyanate can be used. Crude polyisocyanates such as crude toluene diisocyanate obtained by phosgenation of a toluenediamine mixture or crude diphenylmethane diisocyanate obtained by phosgenation of crude methylenediphenylamine may also be used in the practice of embodiments of the present invention. TDI / MDI blends may also be used.

Examples of aliphatic polyisocyanates include ethylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane 1,4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane , Isophorone diisocyanate (IPDI), 1,4-bis (isocyanatomethyl) cyclohexane, saturated analogs of the above aromatic isocyanates, and mixtures thereof. ADI.

The number of functional groups in the isocyanate is preferably greater than 1.0, more preferably greater than 1.5, and most preferably 2 or greater.

A suitable TDI product is the product name VORANATE® and The Dow.
Available from the Chemical Company. A suitable commercial product of that type includes VORANATE® T-80, also available from The Dow Chemical Company. Suitable MDI products are PAPI
(Registered trademark), VORANATE (registered trademark), and ISONATE (registered trademark) are available from The Dow Chemical Company.

The isocyanate can have a functional group number of at least greater than 1, preferably greater than 1.2, more preferably greater than 1.8.

The capping reaction can be carried out at an isocyanate index from about 100 to about 250. All individual values and subranges from 100 to 250 are included herein and disclosed herein. For example, the isocyanate index is 100, 105
110, 125, 140, 150, 160, 170, 175, 180, 190, 200
The lower limit value of 225 can be independently set to the upper limit value of 150, 175, 200, 225, or 250. In some embodiments, the index can be between about 160 and about 200, between about 140 and about 170, or between about 150 and about 180.

In the practice of embodiments of the present invention, the use of a catalyst is not necessary when the hydrosilylated polymer is reacted with a coupling agent, such as a compound having two or more isocyanate groups in each molecule. In certain embodiments, it may be preferable to perform the capping reaction without a catalyst (eg, no catalyst). It has been found that performing the capping reaction without a catalyst results in a reduction of by-products (eg, aliphanate and isocyanurate) in the capped material. However, a catalyst may be used to increase the reaction rate or to improve the degree of conversion. Catalysts to be used in conducting coupling reactions using polyisocyanate compounds include, but are not limited to, for example, Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saun
Mention may be made of the catalysts mentioned in ders and Frisch, Interscience Publishers, New York, 1963.

Preferred urethane-forming reaction catalysts that can be used when performing a coupling reaction using a polyisocyanate compound for high activity are stannous octylate, stannous stearate, dibutyltin dioctoate, dibutyltin Rail malate, dibutyltin dibutylmalate, dibutyltin dilaurate, 1,1,3,3-tetrabutyl-1,
3-dilauryloxycarbonyl distanoxane, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin bis (o-phenylphenoxide), dibutyltin oxide, dibutyltin bis (triethoxysilicate), dibutyltin distearate, dibutyltin bis (isononyl 3- Mercaptopropionate), dibutyltin bis (isooctyl thioglycolate), dioctyl tin oxide, dioctyl tin dilaurate, dioctyl tin diacetate, and dioctyl tin diversatate. Furthermore, it is preferable to use a catalyst having low activity for the crosslinkable silyl group,
Thus, for example, sulfur atom-containing tin catalysts such as dibutyltin bis (isononyl 3-mercaptopropionate) and dibutyltin bis (isooctylthioglycolate) are particularly preferred.

The coupled isocyanate capped polymer can be coupled with a copolymerized polyol to form the final copolymerized silane terminated polymer (cPP-STP).

Polyol with copolymer:
Copolymerized polyols suitable for use according to the invention described herein are well known and widely used on a commercial scale. Copolymer-containing polyols are usually produced by polymerizing one or more ethylenically unsaturated monomers dissolved or dispersed in a polyol (feedstock polyol) in the presence of a free radical catalyst and are stable in the polyol. A dispersion of polymer particles is formed.

Exemplary feedstock polyols include ethylene oxide, propylene oxide, such as polypropylene oxide polyol end-capped with ethylene oxide,
Polyether polyols derived from butylene oxide, tetramethylene oxide, or combinations thereof are included. Any polyol can be used regardless of molecular weight. The molecular weight of the polyether polyol is preferably from 1,000 g / mol to 10,
000 g / mol, more preferably 2,000 g / mol to 8,000 g / mo
l, most preferably in the range of 2,000 g / mol to 6,000 g / mol. The number of functional groups of the polyol is preferably in the range of 1.1 to 8, more preferably in the range of 1.5 to 6, and most preferably in the range of 2 to 4. Feedstock polyols are also
A blend of two or more polyols may be used.

The dispersed phase of the copolymer polymer is produced by in situ polymerization of at least one vinyl monomer. Suitable ethylenically unsaturated monomers are known to those skilled in the art, for example, US Pat. No. 3,931,092 and US Pat. No. 4,521,546, the disclosures of which are hereby incorporated by reference. And those disclosed in the issue. Examples of typical monomers include vinyl chloride, methyl methacrylate, α-methyl styrene, p-methyl styrene, methacrylonitrile, vinylidene chloride, styrene, acrylonitrile, hydroxyethyl acrylate, butadiene, isoprene, chloroprene and methacrylo Nitrile is included. Preferred vinyl monomers are styrene and acrylonitrile. Mixtures of vinyl monomers, for example a weight ratio of 80:20 to 20:80, more preferably 70:
A mixture of 30-30: 70, most preferably 65: 35-35: 65 styrene and acrylontrile can be used. Vinyl monomer mixtures containing 50% by weight or more of styrene with one or more monomers other than styrene can be used. The amount of monomer (s) will give a solids content of 40-80% by weight,
Generally selected. The particle size distribution of the solid may be multimodal. The particle size of the solid can be 0.1 to 10 microns.

The polymerization of the vinyl monomer is generally performed using a polymerization catalyst. Such catalysts are well known in the art, see for example, US Pat. Nos. 4,521,546 and 4,522,976, the disclosures of which are incorporated herein by reference. Preferably, an azobisalkyl nitrile, such as azobis (isobutyronitrile) (AIBN)
, Azobis (4-cyanovaleric acid), azobis (dimethyl-valeronitrile), preferably AIBN; free radical polymerization initiators such as peroxy compounds such as hydroperoxides, peroxyesters and peroxyketones. A commonly used peroxide catalyst is sold under the trademark TRIGONOX from Akzo Nobel. Other examples include hydrogen peroxide, di (t-butyl) -peroxide, t-butyl peroxydiethyl acetate, t-butyl peroctoate, t-butyl peroxyisobutyrate,
Included are t-butyl peroxypivalate, t-amyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, lauroyl peroxide; cumene hydroperoxide and t-butyl-hydroperoxide. Combinations of polymerization catalysts can also be used. The amount of catalyst will vary based on the type of catalyst and the amount of ethylenically unsaturated monomer.

In order to produce a dispersion of polyurethane-urea particles (PIPA) or urea particles (PHD) in a polyol blend, PIPA or PHD forming monomers are dissolved in the polyol blend. If a PHD polymer polyol is desired, PHD-forming monomers can include ammonia, anilines and substituted anilines, and amines such as aliphatic amines. The PHD-forming monomer can also include diamines such as ethylene diamine, 1,6-hexamethylene diamine, alkonolamine, and hydrazine.

If a PIPA polymer polyol is desired, the PIPA-forming monomer is a diol such as glycol; and monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 2- (2-aminoethoxyethanol), hydroxyethylpiperazine, monoisopropanolamine , Alkanolamines such as diisopropanolamine and mixtures thereof. Other alkanolamines that may be considered include N-methylethanolamine, phenylethanolamine, and glycolamine. It is also possible to provide a mixture of PHD and PIPA-forming monomers to form hybrid PHD-PIPA particles.

At least one PHD and / or PIPA polymer-forming monomer is present in the blend at a concentration of between about 2% to about 40%, preferably between about 5% to about 30% by weight of the total polyol blend weight. Added. All individual values and subranges between about 5 wt% and about 50 wt% are included herein and disclosed herein. For example, the solids content is from a lower limit of 5, 8, 10, 15, 20, 25 or 30% by weight of the weight,
Up to an upper limit of 20, 25, 30, 35 or 40% by weight.

The composition of PIPA and / or PHD particles is not only dependent on the monomer structure. That is, the composition of the polyol blend can also affect the particle composition. A polyol such as glycerol, and an amine having only an alcohol such as triethanolamine incorporates polyurethane into the particle, and an amino alcohol such as triethanolamine incorporates polyurethane-urea into the particle, primary or such as hydrazine or ethylenediamine. Secondary amines incorporate polyurea into the particles. The other monomer can be water and additionally forms polybiurets and polyallophanates. Usually, isocyanate-reactive particles are obtained by setting an under-index, i.e., using less polyisocyanate than the theoretical amount required to fully react the monomer. Further, the polymer itself can contain reactive groups such as, for example, polyurea, which are not as reactive as hydroxyl or secondary amine moieties.

Further, the catalyst may be combined with a polyol blend. The organometallic compound can be used in catalytic amounts. Organometallic compounds useful as catalysts include bismuth, lead, tin,
Compounds such as titanium, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese, zirconium are included. Some examples of such metal catalysts include bismuth nitrate, bismuth neodecanoate, lead 2-ethylhexanoate, lead benzoate, lead oleate, dibutyltin dilaurate, tributyltin, butyltin trichloride, dimethyltin, stannic chloride, Examples include stannous octoate, stannous oleate, di (2-ethylhexanoic acid) dibutyltin, ferric chloride, antimony trichloride, antimony glycolate, tin glycolate, iron acetylacetonate, and the like. The catalyst can facilitate the reaction of the diisocyanate with the primary hydroxyl group of the alkanolamine.

Under stirring, at least one isocyanate is added to the polyol blend. Agitation can occur in a stirred reactor or by using a series of static mixers, as is known in the art. Isocyanates that can be used in the present invention include aliphatic, cycloaliphatic, arylaliphatic, and aromatic isocyanates.

Examples of suitable aromatic isocyanates include diphenylmethane diisocyanate (MDI)
4,4'-, 2,4 'and 2,2'-isomers thereof, blends thereof and polymeric and monomeric MDI blends, toluene-2,4- and 2,6-diisocyanate (T
DI), m- and p-phenylene diisocyanate, chlorophenylene-2,4-diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanate—
3,3'-dimethyldiphenyl, 3-methyldiphenyl-methane-4,4'-diisocyanate and diphenyl ether diisocyanate, and 2,4,6-triisocyanatotoluene and 2,4,4'-triisocyanatodiphenyl ether It is.

Isocyanate mixtures such as the commercially available 2,4- and 2,6-isomer mixtures of toluene diisocyanate can be used. Crude polyisocyanates such as crude toluene diisocyanate obtained by phosgenation of a toluenediamine mixture or crude diphenylmethane diisocyanate obtained by phosgenation of crude methylenediphenylamine may also be used in the practice of the present invention. TDI / MDI blends may also be used.

Examples of aliphatic polyisocyanates include ethylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane 1,4-diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, saturated analogs of the above aromatic isocyanates, and A mixture of

Isocyanate index is between about 50 and about 120, between about 60 and about 110, or 6
At least one isocyanate, between about 30 and about 150, such as between 0 and 90, is added to the polyol blend. The isocyanate index may be kept below 100 to minimize isocyanate reaction with the polyol. Isocyanate index is the ratio of isocyanate groups to isocyanate-reactive hydrogen atoms present in the formulation,
Given as a percentage. Thus, the isocyanate index represents the percentage of isocyanate actually used in the formulation relative to the amount of isocyanate theoretically required to react with the amount of isocyanate-reactive hydrogen used in the formulation.

At least one PHD and / or PIPA polymer-forming monomer and isocyanate can successfully carry out the reaction without applying external heat and atmospheric pressure, but higher temperatures and pressures can also be tolerated. . For example, the reaction temperature is about 25 ° C.
To about 100 ° C. and the pressure can range from atmospheric to about 100 psi gauge pressure.

Exemplary copolymerized polyols include SPECFLEX ™ polyol and V
The Dow Chemical under the trade name ORANOL ™ polyol.
Available from Company. Examples of such polyol commercial products are SpecFl.
ex® NC701, IP950S3, experimental copolymer polyol catalyzed by DMC, and VORANOL ™ PP 3039.

The resulting NCO cap prepolymer is exposed to a coupling reaction, in which case
The NCO cap prepolymer was reacted with the copolymer polyol for 2 hours at 70 ° C. in the presence of DABCO T-12 catalyst (or dimethyltin dineodecanoate, Metatin catalyst) to produce a silane-terminated copolymer polyol.

Curing According to embodiments of the present invention, the resulting silane-terminated polymers are allowed to react with each other to further extend the molecular chain length for use such as sealants, adhesives and coatings, and combinations thereof. Especially useful. When the silyl polymer is exposed to moisture, such as moisture from the atmosphere, the hydrolyzable groups bonded to the silicon atoms are hydrolyzed and replaced with silicon-bonded hydroxyl groups. In turn, the hydroxyl groups react with each other or with other hydrolyzable groups to form siloxane (Si-O-Si) linkages. By this method, the polymer molecules of the composition of the embodiments of the present invention are joined together to form an infusible elastomeric material.
To avoid premature curing, the compositions of embodiments of the present invention can be stored and maintained in the absence of moisture until curing is desired. The polymer is then exposed to air or other moisture when curing is desired.

Furthermore, the curing reaction of the silyl polymer can be accelerated by the use of a tin-free silanol condensation catalyst or a curing accelerator. Silanol condensation catalysts or promoters are described in US 6,355.
127, etc., which are well known in the art, including: Titanate such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin malate, dibutyltin diacetate, tin octylate, tin naphthenate, dimethyltin dineodecanoate (Metatin catalyst), dibutyltin oxide and phthalate Reaction products of acid esters, organotin compounds such as dialkyltin diacetylacetonate (such as dibutyltin bis (acetylacetonate)); dialkyltin oxides such as dibutyltin oxide; organic such as aluminum trisacetylacetonate, aluminum trisethylacetonate Aluminum compound; tris (2-ethylhexanoic acid) bismuth,
Reaction products such as bismuth salt (neodeconate) such as bismuth salts and organic carboxylic acids; chelating compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; butylamine, octylamine, dibutylamine, monethanolamine, Examples include amine compounds such as diethanolamine, triethanolamine, diethylenetriamine, cyclohexylamine, and benzylamine, or salts thereof with carboxylic acid. These compounds are not limited. That is, any commonly used silanol condensation catalyst can be used. These silanol condensation catalysts may be used individually or in combination. Such catalysts and promoters include tetrabutyl titanate, dibutyltin dilaurate, dibutyltin bis (acetylacetonate), and the like. The catalyst is at least about 0.1% by weight of the polymer, at least about 0.5% by weight of the polymer, at least about 1% by weight of the polymer, at least about 1.5% of the polymer.
% By weight, or at least about 2% by weight of polymer, and up to about 8% by weight of polymer, up to about 6% by weight of polymer, up to about 5% by weight of polymer, up to about 4% by weight of polymer, or based on polymer weight And can be present in an approximate amount of up to about 3.5%. Such catalysts can be combined with the polymer by means within the skill in the art during the formulation of the sealant, dressing or adhesive.

The resulting cured silyl polymer is also an embodiment of the present invention. Similarly, embodiments of the present invention include sealants, adhesives and dressings and other end use products containing such polymers or prepolymers. The preferred properties of the silyl polymer may vary slightly from end use to end use, and other components optionally present in the composition suitable for each end use may vary as well.

The synthesized cPP-STP can be cured by hydrolysis reaction with moisture and is therefore environmentally friendly and free of isocyanate monomers. The cPP-STP can be cured with the aid of catalyst (s) such as tin-based catalyst, tin-free acid catalyst, or amine catalyst. The final cured material has a higher tensile strength and modulus than an equivalent system that does not contain a copolymer. There may also be an additional benefit that, as is the case with silane-terminated cPP-STP, the moisture uptake of the cured polymer is statistically lower than systems made without using filled polyethers. .

In one embodiment, the method comprises (1) a step of producing an alkoxysilyl-terminated monool by a hydrosilylation reaction between a vinyl-terminated monool and an alkoxysilane in the presence of a catalyst; Capping the alkoxysilyl-terminated monool with an isocyanate (such as TDI (toluene diisocyanate)) in the order of adding to the isocyanate at a temperature of 1 (eg, 60 ° C.) and at a constant rate and then adding the catalyst. including. The reaction is completed at a second temperature (eg, 85 ° C.) to produce an isocyanate cap prepolymer consisting of 2.69-3.18% NCO, and (3) the isocyanate cap prepolymer and copolymerized STP is produced by a coupling reaction obtained by reacting with a polyol. In certain embodiments, the vinyl-terminated monool is 0-4.7 × 10 ⁻³ mgKOH / g, preferably 0-1.9 × 10 ⁻³ mgKOH / g, more preferably 0-1.4 × 10 ^{−. 3} mgKOH
/ G, most preferably 0 to 1.0 × 10 ⁻³ mg KOH / g basic.

The objects and advantages of the embodiments described herein are further illustrated by the following examples. The specific ingredients, and their amounts, as well as other conditions and details listed in these examples should not be used to limit the embodiments described herein. Examples of the present invention are identified by a sample number following the letter “E”, while comparative samples that are not examples of the present invention are indicated by a sample number following the letter “C”.

The description of the raw materials used in the examples is as follows.
Acclamim Polyol 4200
A bifunctional polyether polyol based on propylene oxide having a molecular weight of about 4000 and a hydroxyl number of 26.5 to 29.5 mg KOH / g, available from Bayer MaterialScience.

Acclaim Polyol 6300
Triol based on propylene oxide having a molecular weight of about 6000 and a hydroxyl number of 26.5 to 29.5 mg KOH / g, available from Bayer MaterialScience.

The D under the trade name Allyl Monool UCON ™ Hydrolube APPG 800
commercially available from ow Chemical Company, having an allyl content of 3.5% by weight (unsaturation 0.998 mol / monool 1 mol), a number average molecular weight of about 800, and an OH number of 70 or 2.1% by weight OH Propylene glycol monoallyl ether.

DABCO T-12
Dibutyltin dilaurate catalyst available from Air Products.

DBTA
Dibutyltin bis (acetylacetonate), available from SIGMA-ALDRICH®.

DDBSA
Dodecylbenzenesulfonic acid. Available from SIGMA-ALDRICH®.

VORANOL ™ PP 3039
Graft polyether diols containing copolymerized styrene and acrylonitrile, commercially available from The Dow Chemical Company.

Karstedt's catalyst Platinum-divinyltetramethyldisiloxane available from Gelest, Inc. and xylene as a carrier solvent, the platinum loading in the catalyst being 2 wt%.

Methyldimethoxysilane Available from Gelest, Inc.

SnAcAc
Acetylacetonate tin (II) available from SIGMA-ALDRICH®.

SPECFLEX NC701
Graft polyether triol polyol containing copolymerized styrene and acrylonitrile available from The Dow Chemical Company.

TOYOCAT-DB30
Acid-blocked tertiary amine (1,8-diazabicyclo [5.4.0] undec-7-ene) catalyst available from Tosoh Corporation.

VORANATE ^* T-80
Toluene diisocyanate (80% by weight of 2,4-toluene diisocyanate and 20% by weight of 2,6-toluene diisocyanate) composition available from Dow Chemical Company.

Zinc octylate available from Shepherd Chemical Corporation.

Test method:
The tensile strength was measured according to ASTM standard test D1708. Elongation at break is ASTM
Measured according to standard test D1708. According to 100% ASTM standard test D1708,
Four dogbone samples were prepared and analyzed for mechanical properties. Results are reported as the average of 4 samples, including standard deviation. The number average molecular weight was determined by gel permeation chromatography using a PEG standard product according to ASTM standard test D5296. Viscosity is T
Measurements were made using an A Instruments rheometer AR2000. About 1 mL of the sample was dispensed into a conical plate shape having a diameter of 60 mm and 60 °. After removing any excess material, the viscosity test was performed by heating the sample from 20 ° C. to 100 ° C. at 3 ° C./min. The shear rate of the test was kept at a constant value of 0.1 s- ¹ .

Hydrosilylation:
The hydrosilylation reaction was carried out using propylene glycol monoallyl ether (343.20 g,
800 MW) was carried out by charging a pre-dried 4-neck 250 mL glass reactor equipped with a mechanical stirrer. Next, under a continuous purge of nitrogen, Karstedt catalyst (about 0.03 g) was added to the reactor and mixed for 2 minutes. Methyldimethoxysilane (50.02g
, 106 MW) was added last and mixed for 5 minutes before the entire reactor was heated to 60 ° C. for 2 hours. The hydrosilylation product (hereinafter referred to as hydrosilylation polyether) was analyzed using ¹ H and showed hydrosilylation efficiency> 95%.

Prepolymer synthesis (NCO capping):
The hydrosilylated polyether (299.8 g) is then reacted with excess VORANATE ™ T-80 (49.00 g) for a minimum of 6 hours at 85 ° C. and 300 rpm mixing speed to yield an NCO cap prepolymer. Generated.

Coupling:
The NCO cap prepolymer obtained above is exposed to a coupling reaction, in which case the NCO cap prepolymer is cPP polyol (VORANOL ™) in the presence of DABCO T-12 catalyst at 70 ° C. for 2 hours. PP 3039 or SPECFLEX
NC701) to produce a copolymerized silane-terminated polyol.

Curing:
Curing of the copolymerized silane-terminated polyol can be accomplished in the presence of moisture by tin acetylacetanoate (SnAcAc), dodecylbenzenesulfonic acid (DDBSA) or DB-30.
This was achieved by adding an acrylic acid blocked amine catalyst. A film of silane-terminated polymer material is stretched on a polypropylene sheet to a thickness of 25 mils, 2
Cured at 5 ° C and 50% relative humidity for a minimum of one week. According to ASTM D1708, I
The physical properties of the film were measured using an NSTRON instrument.

Table I shows the components involved in the coupling reaction for Examples 1 to 3 (E1, E2 and E3), and for Control 1 and Control 2. As shown in Table I, Examples 1-3 are based on polyols with IP950-S3 copolymer, and Controls 1 and 2 are based on Acclaim 2200 polyether polyols.

Table II shows Examples 4 to 5 (E4, E5 and E6) and Control 3 (C3)
, The components involved in the coupling reaction are shown. As shown in Table II, Examples 4 and 5 are based on a polyol with SPECFLEX NC701 copolymer and Control 3 is based on an Acclaim 6300 polyether polyol.

A dogbone molded sample of each elastomer having a width of 0.815 inches and a length of 0.827 inches was prepared. The hydrolytic stability of each sample was measured by immersing the elastomer dogbone in boiling water (100 ° C.) for 1 week. The results are shown in Table III and Table IV.

As demonstrated in Table III, Examples 1-3 made using polyols with VORANOL ™ PP 3039 copolymer were superior to Controls 1 and 2 made using Acclaim 4200 polyols. Tensile and modulus properties,
As well as equivalent elongation characteristics.

As demonstrated in Table IV, Examples 4-5 made using a polyol with SPECFLEX NC701 copolymer show superior tensile properties and modulus compared to Controls 1 and 2 made using Acclaim 6300 polyol. The properties as well as equivalent elongation properties were shown.

FIG. 1 is based on a polyol with VORANOL ™ PP 3039 copolymer formed according to embodiments described herein, versus a silane-terminated polyether based on Acclaim 4200 polyether polyol (Controls 1 and 2). FIG. 100 is a diagram comparing water uptake after a water aging test of silane-terminated polymers (Examples 1 to 3). Example 2 (acid catalyzed curing) and Example 1 (tin catalyzed curing) are control 1
Compared to 2 and 2, the water uptake is lower.

FIG. 2 is a diagram 200 comparing the water uptake after a water aging test of a silane-terminated polymer based on SPECFLEX NC701 (Examples 4-6) formed according to embodiments described herein. is there. As demonstrated in FIG. 2, Example 4 (curing with tin catalyst)
And Example 5 (curing with an acid catalyst) is compared to Example 6 (curing with an amine catalyst),
Results showing lower water uptake.

By using a copolymerized polyol in the silane-terminated polymer, the modulus can be significantly improved without substantially losing other properties such as elongation. In addition, the copolymerized polyol can participate in the formation of the polymer matrix;
As a result, it provides superior long-term stability compared to conventional fillers. The use of a copolymerized polyol in a silane terminated polymer also improves processability by eliminating the need to add additional fillers to the system.

While the foregoing is directed to embodiments of the invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof.

While the foregoing is directed to embodiments of the invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof.
The present invention includes the following aspects.
[1]
A composition comprising a copolymerized crosslinkable silane-terminated polymer having at least one crosslinkable silyl group in each molecule, wherein the copolymerized crosslinkable silane-terminated polymer comprises:
A polyol containing a copolymer;
Isocyanate-capped hydrosilylated polymer
Is a reaction product of
The isocyanate-capped hydrosilylated polymer is
At least one isocyanate;
Hydrosilylated polymer
Reaction products with
The hydrosilylated polymer is
A polymer having at least one unsaturated group and at least one alcohol group in each molecule;
Compound having hydrogen-silicon bond and crosslinkable silyl group in each molecule
Including reaction products with
Composition.
[2]
The composition of [1] above, wherein the hydrosilylated polymer is reacted with the isocyanate having an isocyanate index between about 100 and about 250.
[3]
The composition of [1] or [2] above , wherein the hydrosilylated polymer is a reaction product of at least about 70% hydrosilylation efficiency as determined by ¹ H-NMR.
[4]
[1] to [3] above, wherein the polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule has a number average molecular weight between about 100 and about 5,000. Composition.
[5]
Propylene glycol wherein the polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule has a number average molecular weight between 600 and 1,000, and an OH number between 50 and 90 The composition according to the above [1] to [4], which is monoallyl ether.
[6]
The copolymer-containing polyol is
A polyether polyol matrix, and
Solid phase copolymer
The composition according to any one of [1] to [5] above.
[7]
The composition of [6] above, wherein the polyether polyol matrix is derived from ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and combinations thereof.
[8]
[6] or [6], wherein the solid phase copolymer is at least one of copolymerized styrene and acrylonitrile, styrene-acrylonitrile, acrylonitrile, polyurea (PHD) polymer solid, and polyurethane-urea particles (PIPA). 7].
[9]
A method of producing a composition comprising a copolymerized crosslinkable silane-terminated polymer having at least one crosslinkable silyl group in each molecule comprising:
Providing a polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule and having a number average molecular weight between about 100 and about 5,000;
Adding a compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule, and a hydrosilylation catalyst to the polymer, thereby performing a hydrosilylation reaction to form a composition comprising the hydrosilylated polymer;
Capping the hydrosilylated polymer by exposing the hydrosilylated polymer to at least one isocyanate having an isocyanate index between about 100 and about 250 to form a composition comprising the isocyanate-capped hydrosilylated polymer; And
Reacting the isocyanate-capped hydrosilated polymer with a copolymerized polyol to form a composition comprising a crosslinkable silane-terminated polymer;
Manufacturing method.
[10]
The method of [9] above , wherein the hydrosilylation reaction has a hydrosilylation efficiency of at least about 70% as determined by ¹ H-NMR.
[11]
[9] or [10] above, wherein the polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule has a number average molecular weight between about 800 and about 2,000 g / mol. The method as described in any one of.
[12]
A polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule has a number average molecular weight between about 600 and about 1000 and an OH number between about 50 and about 90. The method according to any one of [9] to [11] above, comprising allyl ether.
[13]
The method according to any one of [9] to [12] above, wherein the isocyanate index is between about 160 and about 200.
[14]
The method of any one of [9] to [13] above, wherein the hydrosilylation efficiency is at least about 85%.
[15]
The compound having a hydrogen-silicon bond and a crosslinkable silyl group is at least trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethylsiloxymethylmethoxysilane, and trimethylsiloxydiethoxysilane. The method according to any one of [9] to [14] above, comprising one.
[16]
The isocyanate is at least one of 4,4′-, 2,4 ′ and 2,2′-isomers of diphenylmethane diisocyanate, 2,4-toluene diisocyanate and 20% 2,6-toluene diisocyanate, or blends thereof. The method according to any one of [9] to [15] above, comprising:
[17]
The method according to any one of [9] to [16], wherein the crosslinkable silane-terminated polymer is cured with an amine-containing catalyst to form a cured polymer.
[18]
The method according to any one of [9] to [17] above, wherein the step of capping the hydrosilylated polymer is a non-catalytic reaction.
[19]
The method according to any one of [9] to [18], wherein the composition containing a crosslinkable silane-terminated polymer is cured with a tin catalyst.
[20]
An article comprising the crosslinkable silane-terminated polymer according to the above [9] to [19].
[21]
The article according to [20] above, which is an elastomer, a sealing material, an adhesive, a coating material, or a combination thereof.

Claims (21)

A composition comprising a copolymerized crosslinkable silane-terminated polymer having at least one crosslinkable silyl group in each molecule, wherein the copolymerized crosslinkable silane-terminated polymer comprises:
A polyol containing a copolymer;
A reaction product with an isocyanate-capped hydrosilylated polymer;
The isocyanate-capped hydrosilylated polymer is
At least one isocyanate;
A reaction product with a hydrosilylated polymer,
The hydrosilylated polymer is
A polymer having at least one unsaturated group and at least one alcohol group in each molecule;
A reaction product with a compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule;
Composition. The composition of claim 1, wherein the hydrosilylated polymer is reacted with the isocyanate having an isocyanate index between about 100 and about 250. The hydrosilylated polymer is at least about 70 as determined by ¹ H-NMR.
3. A composition according to claim 1 or 2 which is a reaction product of% hydrosilylation efficiency. The polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule has a number average molecular weight between about 100 and about 5,000,
The composition according to claim 1. Propylene glycol wherein the polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule has a number average molecular weight between 600 and 1,000, and an OH number between 50 and 90 The composition according to claims 1 to 4, which is monoallyl ether. The copolymer-containing polyol is
6. A composition according to claims 1 to 5, comprising a polyether polyol matrix and a solid phase copolymer. The polyether polyol matrix is derived from ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and combinations thereof;
The composition according to claim 6. 8. The solid phase copolymer according to claim 6 or 7, wherein the solid phase copolymer is at least one of copolymerized styrene and acrylonitrile, styrene-acrylonitrile, acrylonitrile, polyurea (PHD) polymer solids, and polyurethane-urea particles (PIPA). The composition as described. A method of producing a composition comprising a copolymerized crosslinkable silane-terminated polymer having at least one crosslinkable silyl group in each molecule comprising:
Providing a polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule and having a number average molecular weight between about 100 and about 5,000;
Adding a compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule, and a hydrosilylation catalyst to the polymer, thereby performing a hydrosilylation reaction to form a composition comprising the hydrosilylated polymer;
Capping the hydrosilylated polymer by exposing the hydrosilylated polymer to at least one isocyanate having an isocyanate index between about 100 and about 250 to form a composition comprising the isocyanate-capped hydrosilylated polymer; And reacting the isocyanate-capped hydrosilylated polymer with a copolymerized polyol to form a composition comprising a crosslinkable silane-terminated polymer. The method of claim 9, wherein the hydrosilylation reaction has a hydrosilylation efficiency of at least about 70% as determined by ¹ H-NMR. 11. The polymer of claim 9 or 10, wherein the polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule has a number average molecular weight between about 800 and about 2,000 g / mol. The method according to one item. A polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule has a number average molecular weight between about 600 and about 1000 and an OH number between about 50 and about 90. 10. Allyl ether is included.
To 11. The method according to any one of 11 to 11. 13. A method according to any one of claims 9 to 12, wherein the isocyanate index is between about 160 and about 200. 14. A method according to any one of claims 9 to 13, wherein the hydrosilylation efficiency is at least about 85%. The compound having a hydrogen-silicon bond and a crosslinkable silyl group is trimethoxysilane,
15. The method according to any one of claims 9 to 14, comprising at least one of triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethylsiloxymethylmethoxysilane, and trimethylsiloxydiethoxysilane. . The isocyanate is at least one of 4,4′-, 2,4 ′ and 2,2′-isomers of diphenylmethane diisocyanate, 2,4-toluene diisocyanate and 20% 2,6-toluene diisocyanate, or blends thereof. Claims 9 to 15
The method as described in any one of. The method of any one of claims 9 to 16, wherein the crosslinkable silane-terminated polymer is cured with an amine-containing catalyst to form a cured polymer. 18. A method according to any one of claims 9 to 17 wherein capping the hydrosilylated polymer is a non-catalytic reaction. 19. A method according to any one of claims 9 to 18, wherein the composition comprising a crosslinkable silane terminated polymer is cured with a tin catalyst.   An article comprising the crosslinkable silane-terminated polymer of claim 1-19. 21. The article of claim 20, wherein the article is an elastomer, a sealant, an adhesive, a dressing, or a combination thereof.

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